CN105063660B - A kind of method that nano-silicon powder is directly prepared in electrorefining processes - Google Patents
A kind of method that nano-silicon powder is directly prepared in electrorefining processes Download PDFInfo
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- CN105063660B CN105063660B CN201510466179.4A CN201510466179A CN105063660B CN 105063660 B CN105063660 B CN 105063660B CN 201510466179 A CN201510466179 A CN 201510466179A CN 105063660 B CN105063660 B CN 105063660B
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- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims description 35
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 65
- 239000000956 alloy Substances 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011863 silicon-based powder Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910016344 CuSi Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000010306 acid treatment Methods 0.000 abstract 1
- 238000010310 metallurgical process Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910000914 Mn alloy Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 235000013312 flour Nutrition 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910021487 silica fume Inorganic materials 0.000 description 3
- -1 wherein Substances 0.000 description 3
- 229910017818 Cu—Mg Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- AIAFIGZLFHZCAD-UHFFFAOYSA-N [Si].[Mn].[Cu] Chemical compound [Si].[Mn].[Cu] AIAFIGZLFHZCAD-UHFFFAOYSA-N 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 239000012686 silicon precursor Substances 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The present invention relates to field of nano material preparation, the method that more particularly to a kind of metallurgical process directly prepares nano-silicon powder body material.The step of the method, includes：SiMe alloys containing Si are electrolysed as anode, negative electrode obtains electrorefining metal Me；The earth of positive pole that electrolysis is produced is collected, earth of positive pole acid treatment is cleaned up after removal metal impurities, with deionized water, that is, obtain the nano-silicon powder that granularity is 20 30nm；In the SiMe alloys, the weight/mass percentage composition of Si is 0.5 13%；Balance of Me.It is low cost of the present invention, simple to operate compared with the existing method for preparing nano-silicon, it is suitable for large-scale production.
Description
Technical field
The present invention relates to field of nano material preparation, nano silica fume is directly prepared in more particularly to a kind of electrorefining processes
The method of body.
Background technology
Nano-silicon has special skin effect and quantum size effect because of it, with characteristics such as more unique light, electricity,
Many performances different from traditional material are shown in terms of energy conversion.Therefore the extensive pass of people is subject in many fields
Note.
At present, preparing the method for nano-silicon mainly has following several.1) quasi- laser ablation：By reactant in laser action
Biochemical reaction is issued, superfine powder is separated out.2) chemical vapor deposition：Make to be pyrolyzed containing silicon precursor in a heated condition,
In the presence of catalyst nano-silicon is deposited in substrate surface.3) magnetron sputtering method：Different from method 2) chemical vapor deposition, this
Method belongs to physical vapour deposition (PVD), typically results in nano thin-film.4) thermal reduction：It is reducing agent to use carbon or magnesium metal,
High temperature is reduced to silica, obtains nano-silicon powder.Except the preparation of the nano silica fume under above-mentioned hot conditions, it is also possible to
Nano-silicon is obtained using wet chemistry method.With monocrystalline silicon as raw material, the attachment of nano-Ag particles is carried out first, then using hydrofluoric acid pair
It carries out chemical etching, you can obtain one-dimensional silicon nanowires.
In the above method, frequently with physics or chemical deposition need to provide laser, plasma or temperature higher
Degree, and apparatus expensive, thus it is relatively costly.During thermal reduction, due to the generation of side reaction, cause the yield of product relatively low,
It is not suitable for large-scale production.Chemical etching method there is also expensive raw material price, and experimental cost is high, and the experiment of use is former
Material has severe corrosive, and reaction solution is not disposable, therefore, it is also unsuitable for the market application of scale.
The content of the invention
The purpose of the present invention is directed to the defect that above-mentioned existing technology is present, in a kind of electrorefining processes of proposition directly
The method for preparing nano-silicon powder, the inventive method has low cost, simple to operate, is suitable for the advantage of large-scale production.
To achieve the above object, patent of the present invention proposes to directly obtain nano silica fume using hydrometallurgy electrorefining processes
Body, its anode is siliceous alloy.
In electrorefining processes, the negative electrode that the metal ingredient in anode alloy can be in electrolysis is deposited, and is easy to metal
Recycling；The anode silicon-containing alloy for being used can be the alloy that silicon is constituted with single metallic element, it is also possible to siliceous
A certain amount of microalloying metallic element is added in alloy, to improve the physical and chemical performance of anode alloy, is optimized it and was electrolysed
Journey.
The method that nano-silicon powder is directly prepared in a kind of electrorefining processes of the present invention, is to make the SiMe alloys containing Si
For anode is electrolysed, negative electrode obtains electrorefining metal Me；Collect electrolysis produce the earth of positive pole, to earth of positive pole removal of impurities after, obtain
To nano-silicon powder；
In the SiMe alloys, Me includes metallic copper or aluminium.
The method that nano-silicon powder is directly prepared in a kind of electrorefining processes of the present invention, in the SiMe alloys, Si's
Weight/mass percentage composition is 0.5-13%；Balance of Me.
The method that nano-silicon powder is directly prepared in a kind of electrorefining processes of the present invention, also includes quality in SiMe alloys
Percentage composition is the microalloying metallic element of 0-4%, and the microalloying metallic element is selected from nickel, iron, manganese, zinc, magnesium
It is at least one.
The method that nano-silicon powder is directly prepared in a kind of electrorefining processes of the present invention, the SiMe alloys are closed for CuSi
The weight/mass percentage composition of Jin Shi, Si is 1-5%, and microalloying metallic element weight/mass percentage composition is 0-4%, balance of Cu.
The method that nano-silicon powder is directly prepared in a kind of electrorefining processes of the present invention, CuSi alloys use following proposal
Prepare：
Alloy target composition by design is with taking Si powder (silicone content more than 98%), Cu powder or with taking metallurgical Si powder, Cu powder
With microalloying metal dust, at least 1 time vacuum melting being carried out first and obtaining master alloy ingot, then master alloy ingot is protected in argon gas
Remelting at least one times is carried out under shield and obtains CuSi alloy anodes；
Vacuum is 10 during vacuum melting-3-10-5Pa, vacuum melting temperature and remelting temperature are 1250-1450 DEG C；
Bath composition is：Content of copper ion 30-60g/L, sulfuric acid content 160-250g/L, content of hydrochloric acid 0.5-1.5mL/
L or KCE content 0.5-1g/L；
Electrolytic process parameter is：Negative electrode is fine copper electrode or stainless steel electrode, 40-65 DEG C of electrolysis temperature, tank voltage 250-
350mV, current density 200-400A/m2, anode and cathode pole span 30-100mm.
The method that nano-silicon powder is directly prepared in a kind of electrorefining processes of the present invention, the SiMe alloys are closed for AlSi
The weight/mass percentage composition of Jin Shi, Si is 1-5%, and microalloying metallic element weight/mass percentage composition is 0-4%, balance of Al.
The method that nano-silicon powder is directly prepared in a kind of electrorefining processes of the present invention, AlSi alloys use following proposal
Prepare：
Alloy target composition by design is with taking Si powder (silicone content more than 98%), Al powder or with taking metallurgical Si powder, Al powder
With microalloying metal dust, at least 1 time vacuum melting being carried out first and obtaining master alloy ingot, then master alloy ingot is protected in argon gas
Remelting at least one times is carried out under shield and obtains CuSi alloy anodes；
Vacuum is 10 during vacuum melting-3-10-5Pa, vacuum melting temperature and remelting temperature are 600-1000 DEG C；
Electrolyte is：In chlorination -1- Toluene-3,4-dithiols-butyl imidazole and AlCl3In molar ratio 1:In the ionic liquid that 1-3 is made into
Add the NH of 0.01-0.05moL/L4The toluene composition of Cl or 0.5-2moL/L；
Electrolytic process parameter is：
Negative electrode is low-carbon (LC) steel or stainless steel,
Electrolysis temperature 55-90,；
Tank voltage 250-500mV,
Current density：50-120A/m2,
Anode and cathode pole span 10-30mm；
Argon gas protection during electrolysis.
The method that nano-silicon powder is directly prepared in a kind of electrorefining processes of the present invention, earth of positive pole removal of impurities is by the earth of positive pole
It is immersed in the acid solution that concentration is 0.1-1mol/L, after removal metal, it is 7 to be cleaned with deionized water to cleaner liquid pH value is crossed；
The acid solution is selected from the mixed acid that hydrochloric acid, nitric acid or hydrochloric acid and nitric acid are mixed to get with arbitrary ratio
Kind.
The method that nano-silicon powder is directly prepared in a kind of electrorefining processes of the present invention, obtains the granularity of nano-silicon powder
It is 20-30nm.
Compared with prior art, the present invention has following remarkable advantage：
(1) vacuum melting twice can be such that silicon enters with parent metal (copper, aluminium and other microalloying metals) with atomic level
Row alloying, silicon crystal grain is tiny and is evenly distributed；By the removal alloying process of electrorefining so that silicon is with extremely small
Grain enters in the earth of positive pole, so as to high-quality nano-silicon powder can be obtained, meets the demand of battery nano-silicon.
(2) anode alloy play the role of further crystal grain thinning comprising micro alloying element, this is to anodic dissolution processes
It is middle to produce the fine grained earth of positive pole containing Si advantageously, also advantageously in acquisition nano-silicon powder.
(3) in electrorefining processes, elemental copper or aluminium are still enriched with the form of fine copper or fine aluminium in negative electrode, because
This, beneficial to reclaiming and recycling, while can also further reduce nano-silicon preparation cost.
(4) the inventive method electrolytic process is easily controllable, with low cost, simple to operate, efficiency high, is suitable for extensive
The advantage of production.
Brief description of the drawings
Accompanying drawing 1 is the XRD of the gained nano-silicon powder of the embodiment of the present invention 1.
Accompanying drawing 2 is the TEM photos of the gained nano-silicon powder of the embodiment of the present invention 1.
Be can be seen that from accompanying drawing 1, the thing phase composition of powder prepared by the embodiment 1 of the inventive method is Si；
From accompanying drawing 2 as can be seen that the particle mean size of the Si powder prepared using the embodiment 1 of the inventive method is left in 30nm
It is right.
Specific embodiment
Embodiment 1：
Step 1：Copper Antaciron is prepared, siliceous 3.5wt% in the alloy, iron content 0.1wt%, balance of copper.Press first
The proportioning of each composition weighs copper powder, silica flour and iron powder in alloy, and by they it is well mixed after be placed in 10-5The vacuum of Pa vacuums
In electric arc furnaces, the melting at 1400 DEG C obtains master alloy ingot after i.e. cooling after whole material meltings.
Step 2：Prepare copper Antaciron anode
The master alloy ingot of gained is carried out into secondary fusion under argon gas protection, in 1400 DEG C, then casting as thickness is
The positive plate of 4mm.
Step 3：Electrorefining
The alloy sheets of step 2 gained are cut into length and width size for 100mm × 60mm, and as anode, with identical
The stainless steel of size is negative electrode, and anode is just right with negative electrode, and electrode spacing is 30mm, and electrolyte is that the sulfuric acid containing copper sulphate is molten
Liquid, wherein, copper content is 50g/L, and sulfuric acid content 180g/L, concentration of hydrochloric acid is 0.5mL/L, and the electric current that electrorefining is used is close
It is 250A/m to spend2, anode electrode plate electrolysis finish, that is, stop electrolytic process.Then it is to obtain anode by electrolyte filtering
Mud.
Step 4：By earth of positive pole pickling.By the salt acid soak of 1mol/L of the earth of positive pole collected by step 3, then with deionization
Water washing is 7 to cleaner liquid pH value is crossed, and is then dried, that is, obtain the present embodiment powder.
Fig. 1 is the XRD test results of the present embodiment gained powder, it is clear that the present embodiment gained powder is Si；Fig. 2 is this
The TEM pictures of embodiment gained powder, it is clear that the particle mean size of the present embodiment gained Si powder is in 30nm or so.
Embodiment 2：
Step 1：Copper silicon manganese alloy is prepared, siliceous 3.5wt%, 3.5wt% containing zinc, 0.5wt% containing manganese, remaining in the alloy
It is copper to measure.Copper powder, silica flour, zinc powder and manganese powder are weighed by the proportioning of each composition in alloy first, and they are well mixed rearmounted
In 10-3In the vacuum arc furnace ignition of Pa vacuums, the melting at 1250 DEG C obtains foundry alloy after i.e. cooling after whole material meltings
Ingot.
Step 2：Prepare copper silicon manganese alloy anode
The master alloy ingot of gained is carried out into secondary fusion under argon gas protection, in 1250 DEG C, then casting as thickness is
The positive plate of 4mm.
Step 3：Electrochemical electrolysis are refined
The alloy sheets of step 2 gained are cut into length and width size for 100mm × 60mm, and as anode, with identical
The stainless steel of size is negative electrode, and anode is just right with negative electrode, and electrode spacing is 30mm, and electrolyte is that the sulfuric acid containing copper sulphate is molten
Liquid, wherein, copper content is 60g/L, sulfuric acid content 190g/L, and carrying out electrolysis using electrochemical workstation removes alloy, the electricity of use
Current density is 220A/m2, anode electrode plate electrolysis finish, that is, stop electrolytic process.Then it is to obtain by electrolyte filtering
The earth of positive pole.
Step 4：By earth of positive pole pickling.By the salt acid soak of 0.1mol/L of the earth of positive pole collected by step 3, then with go from
Sub- water washing is 7 to cleaner liquid pH value is crossed, that is, it is the nano-silicon of 25nm to obtain average grain diameter.
Embodiment 3：
Step 1：Copper silicon zinc-nickel manganese alloy is prepared, siliceous 1wt%, 0.2wt% containing zinc in the alloy, nickeliferous 2.4wt% contain
Manganese 0.1wt%, balance of copper.Copper powder, silica flour, zinc powder, nickel powder and manganese powder are weighed by the proportioning of each composition in alloy first, and will
10 are placed in after they are well mixed-5In the vacuum arc furnace ignition of Pa vacuums, the melting at 1350 DEG C, after after whole material meltings i.e.
Cooling obtains master alloy ingot.
Step 2：Prepare copper silicon manganese alloy anode
The master alloy ingot of gained is carried out into secondary fusion under argon gas protection, in 1350 DEG C, then casting as thickness is
The positive plate of 4mm.
Step 3：Electrochemical electrolysis are refined
The alloy sheets of step 2 gained are cut into length and width size for 100mm × 60mm, and as anode, with identical
The stainless steel of size is negative electrode, and anode is just right with negative electrode, and electrode spacing is 30mm, and electrolyte is that the sulfuric acid containing copper sulphate is molten
Liquid, wherein, copper content is 60g/L, sulfuric acid content 190g/L, and carrying out electrolysis using electrochemical workstation removes alloy, the electricity of use
Current density is 250A/m2, anode electrode plate electrolysis finish, that is, stop electrolytic process.Then it is to obtain by electrolyte filtering
The earth of positive pole.
Step 4：By earth of positive pole pickling.By the earth of positive pole collected by step 3 0.5mol/L hydrochloric acid and 0.5mol/L nitric acid structures
Into nitration mixture immersion, then with deionized water wash to cross cleaner liquid pH value be 7, that is, obtain average grain diameter be 20nm nanometer
Silicon.
Embodiment 4：
Step 1：Al-Si-Cu-Mg manganese alloy is prepared, siliceous 12.6wt% in the alloy, cupric 1wt%, 0.5wt% containing magnesium,
0.5wt% containing manganese, balance of aluminium.First aluminium powder, metallurgical silica flour, copper powder, magnesium powder and manganese are weighed by the proportioning of each composition in alloy
Powder, and by they it is well mixed after be placed in 10-5In the vacuum arc furnace ignition of Pa vacuums, the melting at 950 DEG C treats that whole materials melt
It is that cooling obtains master alloy ingot after change.
Step 2：Prepare Al-Si-Cu-Mg manganese alloy anode
The master alloy ingot of gained is carried out into secondary fusion under argon gas protection, in 750 DEG C, then casting as thickness is
The positive plate of 4mm.
Step 3：Electrochemical electrolysis are refined
The alloy sheets of step 2 gained are cut into length and width size for 100mm × 60mm, and as anode, with identical
The mild steel of size is negative electrode, and anode is just right with negative electrode, and electrode spacing is 10mm, and electrolyte is：Chlorination -1- Toluene-3,4-dithiols -
Butyl imidazole and AlCl3In molar ratio 1:The NH of 0.03moL/L is added in 2 ionic liquids being made into4Cl is constituted；
Electrolytic process parameter is：
Negative electrode is mild steel,
75 DEG C of electrolysis temperature,；
Tank voltage 450mV,
Current density：50A/m2,
Argon gas protection during electrolysis；
Anode electrode plate electrolysis are finished, that is, stop electrolytic process.Then it is to obtain the earth of positive pole by electrolyte filtering.
Step 4：By earth of positive pole pickling.By the earth of positive pole collected by step 3 0.5mol/L hydrochloric acid and 0.5mol/L nitric acid structures
Into nitration mixture immersion, then with deionized water wash to cross cleaner liquid pH value be 7, that is, obtain average grain diameter be 30nm nanometer
Silicon.
Claims (7)
1. a kind of method that nano-silicon powder is directly prepared in electrorefining processes, is to enter the SiMe alloys containing Si as anode
Row electrolysis, negative electrode obtains electrorefining metal Me；Collect electrolysis produce the earth of positive pole, to earth of positive pole removal of impurities after, obtain nano-silicon
Powder；
In the SiMe alloys, Me includes metallic copper or aluminium；
In the SiMe alloys, the weight/mass percentage composition of Si is 0.5-13%；Balance of Me；Also include quality hundred in SiMe alloys
Point content is the microalloying metallic element of 0-4%, and the microalloying metallic element is selected from nickel, iron, manganese, zinc, magnesium at least
It is a kind of；
CuSi alloys are prepared using following proposal：
Match somebody with somebody by the alloy target composition of design and take Si powder, Cu powder or with metallurgical Si powder, Cu powder and microalloying metal dust is taken, it is first
First carry out at least 1 time vacuum melting and obtain master alloy ingot, master alloy ingot is then carried out into remelting at least one times under argon gas protection
Obtain CuSi alloy anodes；
Vacuum is 10 during vacuum melting-3-10-5Pa, vacuum melting temperature and remelting temperature are 1250-1450 DEG C；
AlSi alloys are prepared using following proposal：
Match somebody with somebody by the alloy target composition of design and take Si powder, Al powder or with metallurgical Si powder, Al powder and microalloying metal dust is taken, it is first
First carry out at least 1 time vacuum melting and obtain master alloy ingot, master alloy ingot is then carried out into remelting at least one times under argon gas protection
Obtain AlSi alloy anodes；
Vacuum is 10 during vacuum melting-3-10-5Pa, vacuum melting temperature and remelting temperature are 600-1000 DEG C；
Copper electrolyzing refining bath composition is：Content of copper ion 30-60g/L, sulfuric acid content 160-250g/L, content of hydrochloric acid 0.5-
1.5mL/L or KCE content 0.5-1g/L；
Aluminium electroloysis refines electrolyte：In chlorination -1- Toluene-3,4-dithiols-butyl imidazole and AlCl3In molar ratio 1:The ion that 1-3 is made into
The NH of 0.01-0.05moL/L is added in liquid4The toluene composition of Cl or 0.5-2 moL/L.
2. the method that nano-silicon powder is directly prepared in a kind of electrorefining processes according to claim 1, its feature exists
In：When the SiMe alloys are CuSi alloys, the weight/mass percentage composition of Si is 1-5%, and microalloying metallic element quality percentage contains
It is 0-4% to measure, balance of Cu.
3. the method that nano-silicon powder is directly prepared in a kind of electrorefining processes according to claim 2, its feature exists
In：
Electrolytic process parameter is：Negative electrode is fine copper electrode or stainless steel electrode, 40-65 DEG C of electrolysis temperature, tank voltage 250-
350mV, current density 200-400 A/m2, anode and cathode pole span 30-100mm.
4. the method that nano-silicon powder is directly prepared in a kind of electrorefining processes according to claim 1, its feature exists
In：When the SiMe alloys are AlSi alloys, the weight/mass percentage composition of Si is 0.5-13%, microalloying metallic element quality hundred
Content is divided to be 0-4%, balance of Al.
5. the method that nano-silicon powder is directly prepared in a kind of electrorefining processes according to claim 4, its feature exists
In：
Electrolytic process parameter is：
Negative electrode is low-carbon (LC) steel or stainless steel,
55-90 DEG C of electrolysis temperature；
Tank voltage 250-500mV,
Current density：50-120 A/m2,
Anode and cathode pole span 10-30mm；
Argon gas protection during electrolysis.
6. the side of nano-silicon powder is directly prepared in a kind of electrorefining processes according to claim 1-5 any one
Method, it is characterised in that：Earth of positive pole removal of impurities is that the earth of positive pole is immersed in the acid solution that concentration is 0.1-1mol/L, removes metal
Afterwards, it is 7 to be cleaned with deionized water to cleaner liquid pH value is crossed；
The acid solution is selected from the one kind in the mixed acid that hydrochloric acid, nitric acid or hydrochloric acid and nitric acid are mixed to get with arbitrary ratio.
7. the method that nano-silicon powder is directly prepared in a kind of electrorefining processes according to claim 6, its feature exists
In：The granularity for obtaining nano-silicon powder is 20-30nm.
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